1-Chloroethyl chloroformate → HCID 86610781, compound

HRID 2112751Notes

Reaction equation

HRID 2112751 reaction equation
C([N:8]1[CH2:17][CH2:16][C:15]2[C:14]([NH:18][CH2:19][C:20]3[CH:25]=[CH:24][C:23]([Cl:26])=[CH:22][C:21]=3[Cl:27])=[N:13][C:12]([O:28][S:29]([C:32]3[CH:37]=[CH:36][C:35]([CH3:38])=[CH:34][CH:33]=3)(=[O:31])=[O:30])=[N:11][C:10]=2[CH2:9]1)C1C=CC=CC=1.ClC(OC(Cl)C)=O>ClCCCl.O>[ClH:26].[Cl:27][C:21]1[CH:22]=[C:23]([Cl:26])[CH:24]=[CH:25][C:20]=1[CH2:19][NH:18][C:14]1[C:15]2[CH2:16][CH2:17][NH:8][CH2:9][C:10]=2[N:11]=[C:12]([O:28][S:29]([C:32]2[CH:33]=[CH:34][C:35]([CH3:38])=[CH:36][CH:37]=2)(=[O:31])=[O:30])[N:13]=1

Participants

5

Reactant 2

HCID 5213051-Chloroethyl chloroformateHCID 86610783HCID 86610783, compound

Product 1

HCID 86610781HCID 86610781, compoundYield 53%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 962WaterSolvent

Procedure

7-Benzyl-4-(2,4-dichlorobenzylamino)-2-(4-toluenesulfonyloxy)-5,6,7,8-tetrahydropyrido[3,4-d]pyrimidine (18.7 g, 31.9 mmol) prepared according to Process Step 2 was dissolved in 1,2-dichloroethane (110 mL), and the solution was mixed with 1-chloroethyl chloroformate (14.1 mL), followed by stirring at room temperature for 40 minutes. After checking the completion of the reaction by thin layer chromatography, the reaction mixture was diluted with water, was stirred and was extracted with ethyl acetate. The organic layer was washed with brine, was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=1:1) and thereby yielded a 4-(2,4-dichlorobenzylamino)-7-(1-chloroethoxycarbonyl)-2-(4-toluenesulfonyloxy)-5,6,7,8-tetrahydropyrido[3,4-d]pyrimidine fraction. After distilling off the solvent, the residue was dissolved in methanol (150 mL), followed by stirring at room temperature for two hours. After concentrating the reaction mixture, the residue was mixed with diethyl ether for crystallization. The precipitated crystals were collected by filtration, were dried and thereby yielded 4-(2,4-dichlorobenzylamino)-2-(4-toluenesulfonyloxy)-5,6,7,8-tetrahydropyrido[3,4-d]pyrimidine hydrochloride (7.86 g, in a yield of 53%).

Workup

  1. customthe completion of the reaction by thin layer chromatography
  2. stirringwas stirred
  3. extractionwas extracted with ethyl acetate
  4. washThe organic layer was washed with brine
  5. dry with materialwas dried over anhydrous magnesium sulfate
  6. distillationthe solvent was distilled off
  7. customThe residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=1:1)

Sources & evidence

ORD record
ord-584f4beea43641a1a30219253f5d16d8
Source dataset
uspto-grants-2009_04
Patent number
US07524852B2

Reaction notes

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